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Patented Nov. 13, 1928..

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srrss PATENT FFiCE.

IRVING F. LAUCKS AND GLENN DAVIDSON, OF SEATTLE, WASHINGTON, ASSIGNORS TO I. F. LA'UCKS, INC., OF SEATTLE, WASHINGTON, A CORPORATION OF WASHINGTON.

VEGETABLE GLUE AND METHOD OF MAKING SAME.

No Drawing. Original application filed (lctober 29. 1923, Serial No. 671.381. Divided and this application filed March 9, 1927. Serial N0.-174,093.

The art of making a water-proof glue from certain protein materials has been known for some time; thus casein. and blood albumin are in common use. These last mentioned compounds, however, have a number of disadvantages from a practical standpoint. Casein is costly and lack of uniformity in the material as derived from various sources'is a serious detriment; while blood albumin is not available except in certain situations. There is accordingly a great demand, partic ularly in the veneer industry where large quantities of glue are consumed, for a new glue that will be cheap and at the same time 1 sufficiently water-proof.

By water-proof, in this connection, it is not meant that glues thus characterized will resist the action of water indefinitely, but it is meant that they are water-proof in the sense in which the term is used in the veneer industry, viz, that a panel can be soaked in cold water for from seventy-two to one hundred hours, or in boiling water for eight hours, withoutseparation.

Vegetable compounds have not, so far as we are aware, been heretofore satisfactorily employed as a basis for Water-proof glues of the type in question. It is true that some veneer makers, on account of the high price of casein, have come to use starch glues but these, at least as heretofore made, are not at all water-proof, and vegetable proteins have not heretofore been used at all, so far as we are aware.

We have now discovered, however, that by subjecting the same to proper treatment, such vegetable proteins or vegetable matter containing proteins in proper amount can be converted into a water-proof glue that will sat- 40 isfy the rigid requirements of veneer making. The requisite raw material may be derived from a number of sources and the treatment of such material according to our invention is relatively simple and inexpensive so that as a result we are able to produce a satisfactory glue at a much lower cost than has heretofore been possible.

To the accomplishment of the foregoing and related ends, the invention, then, consists of the combination of ingredients or composition of matter and the steps involved. in the preparation of such composition hereinafter fully described and particularly pointed out in the claims, it being understood that such disclosed ingredients and steps constitute but several of the various ways in which the principle of the invention may be 'used.

" We have found that soya bean flour constitutes an admirable raw material for our purpose. Such flour is preferably made by grinding soya bean cake so that 80 per cent will pass a 100 mesh screen and when treated with certain chemicals, or other substances, we make therefrom a very satisfactory glue that meets the requirements of the veneer trade fully and is in many respects better than the usual glues now on the market. Such bean cake, as analyzed by us, is found to contain on the average 45 per cent protein, 12 per cent water, 5 per cent cellulose or crude fiber, 7 per cent oil, 6 per cent ash, and 25 per cent carbohydrates.

We do not, however, wish to limit ourselves to soya bean flour .or to vegetable protein derived from this source for we have made satisfactory glue by our improved process-from vegetable materials containing protein in amounts intermediate between the percentages thus noted as found in such soya bean flour and wheat or even lower than the percentage in such wheat thatmay be utilized with satisfactory results; that is, soya bean fiour gives the best results, but other sources of vegetable protein-containing material may be employed with proportionately advantageous results.

Soya bean flour made from soya bean cake from .which the oil has beenexpressed, is preferably used in practice because it is cheaper and makes a better glue, but flour made from whole soya beans, without expressing the contained oil, may also be used, although obviously this would not be economical in view of the value which attaches to such oil. As to the fineness of the flour, it is not necessary that the meal be ground as fine as indicated above, but fineness is desirable from a practical standpoint.

lZl hen the usual chemicals employed in making casein glue, viz, lime and sodium silicate, are added to a'vegetable proteincontaining material, for example, flour, a glue results, but it is not as good as casein glue. It is not as highly water resistant nor as workable. We find, however, by the use of caustic-soda with such vegetable protein-containing matter, a much better glued;

is obtained, such caustic soda apparently playing the part of dispersing the colloidal material. The resultant glue is 'then somestill slightly less.

is placed in dilute water solution, it furnishes I an alkaline medium.

hydroxyl ions. Compounds responding to this test are commonly called alkaline compounds and in water solution would provide on our vegetable protein-containing material with both caustic soda and lime. -As equivalents of such caustic soda, caustic potash and ammonia may be used, although more ex:- pensive. Other equivalents of caustic soda are salts of soda (or potash) with weak acids,

e. g. sodium phosphate, sodium borate and Y the like. Similarly in place-of lime, .magnesia, baryta andstrontia may be used as equ valents.

i In order to improve the workingproperresisting' properties, we have found-it desirable to add other substances of which the following are examples a Carbon bisulphide, calcium polysulphide; Equivalents. would be other sulphur compounds .of like properties or constitution, such for example, sodium'thiocarbonate and potassium xanthate, sodiumsilicate, or other soluble silicates.

In general'carbon-bisulphide imparts very great water resistingproperties, as does also calcium polysulphide, although to a lesser degree, that is, for good practical effects sulphur-containing compounds like carbon bis'ulphide which in the composition with the vegetable protein matter provide sulphur de rivatives of carbonic acid are most desirably employed, such sulphur derivatives of 'carbonic acid constituting a regularly recognized classification in standard chemical authorities, such, for example, as Richter, Organic Cl1emistry,1916, Volume I, page l31, and Julius Schmidt,,Organic-Chemistry, page In connection with this general treatment,

-we also bring the vegetable protein-containing matter into a dispersed condition that is;

the sta-teattained in the transformation of a mealy-like or granular mass to a more or less smooth mass 'in the presence of a liquid, and to such extent as we thus refer to the degree of;v subdivision of. particles we believe that we are using the term dispersionnot inconsistently with the accepted usage of colloid chemists.

We have also found that certain substances Preferably we react will act in the same way as the caustic soda and also render the product of a very desirable consistency, e. g. sodium phosphate, sodium perborate' and sodium sulphite. These salts are all related in that they are combinations of the strong base sodium with a weak acid. and there are 'a number of other salts th atfall in the same category and which have a similar effect, so need not be listed in detail.

typical formulae 1. Mix 30 parts. soya. bean flourv with l20 parts'water; add 13 parts of 18 per cent causthen spread on panels, for example, put

under pressure for several hours, whereupon the pressure may be released.

2. ,Dry mix 900 parts peanut flour; parts sodium carbonate; 54 parts lime; and67 parts sodium fluoride; this drymixture is ties, e. g. the spreadingand flow, of the glue added' to 1800 parts of water with stirring produced as aforesaid as well as the water' Example No. 2 excepting cottonseed flour is provides the finished adsubstituted'for'peanut flour; to the dry mixture 1500-parts of water are added and 15' parts lime in 15 part s of water and 90' parts of sodium thiocarbonate solution; to thismixture is added 1900 parts of water,

stirring Y the same as in Example 2; the sodium thiocarbonate solution is prepared by dissolvmg 320 parts of 60lper cent sodiumsulphide in 1000 parts of water and adding 260 parts of carbon bisulphide.

4. Dry mix 300 parts of soya bean flour;

65 parts of lime; 30 parts of sodium carbon-- ate; 22 parts of sodium fluoride; and 10 parts o'fboric acid; to this dry-mixture is then added 650 parts of water with stirring; then 25 parts of potassium xanthate is added with stirring; next is added; 400 parts of water with stirring which stirring is continued for about ten minutes.

,The particular order in which the several ingredients are admixed together in the formulae just given may be varied and it is not necessar be comp but as a that the manufacture of the product matter of practice we have found it desirable in certain. cases to mix only certain of the ingredients initially and then add the others just before the glue is required foruse,

eted in asingle continuous operation,

. 4 y p 75 As examples we may cite the following 100 3. Thedry mixture is the same here as in employed in carrying out such process prov vided the stated ingredients and steps or the equivalent of such stated ingredients or V proportion of a sulphur-containing comthat is, the dry ingredients or, as the same may be called, the dry mix of the above examples may be supplied to the user unassocia-ted with the liquid ingredients and the liquid ingredients then added by the user at the time he wishes to prepare the adhesive.

It will also be understood, of course, that the foregoing formulae are typical and that many variations are actually made therein in 'the compounding of our improved glue.

This application is a division of our application, Serial No. 671,381, filed Oct. 29, 1923.

Other modes of applying the principle of our invention-may be employed instead of the one explained, change being made as regards the process herein disclosed or the materials steps be employed.

We therefore particularly point out and distinctly claim as our invention 1. An adhesive wh'ch comprises tion products of vegetable protein matter, an aqueous alkaline medium, and a small-pro portion of a sulphur-containing compound which provides a sulphur derivative 'ot'carbonic acid.

'2. An adhesive pound which provides a sulphur derivative of carbonic acid.

3. An adhesive which comprises'the reaction products of vegetable protein matter, an aqueous caustic soda-lime medium, and a small proportion of a sulphur-containing compound which provides a sulphur derivative of carbonic acid;

4. An adhesive which comprises the reaction products ofsoya bean protein matter, an aqueous alkaline medium, and a small pro- 4 portion of a sulphur-containing compound which provides a sulphur derivative of carbonic acid. A

5. An adhesive which comprises the reaction products of soya bean protein matter,

an aqueous caustic soda medium, and a small pound which provides a sulphur derivativeof carbonic acid.

6 An adhesive which comprises the reaction products of soya bean protein matter,

an aqueous caustic soda-lime medium, and a small proportion of a sulphur-containing compound which provides a sulphur derivative of carbonic acid. a

7. An adhesive whichcomprises the reaction products of vegetable protein matter,

an aqueous alkaline medium, and a small proportion of carbon bisulphide.

8. An adhesive which comprises the reaction products of vegetable protein matter,

the reacwhich comprises the reac-I. tion products of vegetable protein matter, 'an' aqueous caustic soda medium, and-aasma-ll proportion of a sulphur-containingjcom 17. In an aqueous soya an aqueous caustic soda medium, and a small proportion of carbon bisulphide.

9. An adhesive'which comprises the re- 12. An adhesive which comprises the re-' action products of soya bean protein matter, an aqueous caustic soda-lime medium, and a small proportion of carbon bisulphide.

13. An adhesive which comprises the react-ionproducts of soya bean flour, an aqueous alkaline medium, and carbon bisulphide as a water-proofing agent.

14:. An adhesive which comprises the reaction products of soya bean flour, an aqua-- ous-alkaline medium, and carbon bisulphide,

' the carbon bisulphide and the soya bean flour being inthe proportions'of about five parts and about thirty parts respectively. 15. In an aqueous vegetable protein-con- .taini-ng adhesivean ingredient whichfunctions as a water-resistance-increasing agent, the same being the reaction product of a sul- .phur-containing compound which provides a sulphur derivative of carbonic acid.

16. In an aqueous vegetable protein-comlUU taining adhesive an ingredient which functions as a water-resistancesincreasing agent,

the same being the reaction product of carbon bisulphide therewith.

taining" adhesive an ingredient which functions as a water-reslstance-lncreaslng agent,

bean protein-com the same being the reaction product of a sulphur-containing compound which provides a sulphur derivative of carbonic acid.

18. In an aqueous soya bean protein-containing'adhesive an ingredient which.func-' tions as a water-resistance-increasing agent, the same being the reaction product of carbon 'blsulphlde therewlth.

19. In the process of making an adhesive, 1

the step of reacting upon alkaline treated vegetable protein matter in an aqueous'medium with a small proportion of a sulphure containing compound which provides a sulphur derivative of carbonic. acid.

20. In the process of making an adhesive,

the. stepzo'f reacting upon alkaline treated vegetable protein matter in an aqueous medlum with a smallproportion of carbon bisulphide.

21. In the process of making. an adhesive,

the step of reacting upon alkaline treated.

soya bean protein matter in an aqueous medium with a small proportion of a' sulphurphur de sulphide.

contain nglcom'pound which provides a sulrivative of carbonic acld. 4

22. In the process of making an adhesive,

the step of reacting upon alkaline treated soya bean protein matter in an aqueous medium with a small proportion of carbon b1 an adhesive,

23. The process of makin fie protein matcomprising subjecting vegetab ter to an aqueous alkaline medium of a,

strength which will chemically react with such protein matter in the presence of a small proportion of a sulphur-containing co mpound which provides a'sulphur derivative of carbonic acid.

24. The process of making an adhesive, comprising reacting upon vegetable protein matter in an aqueous caustic soda medium witha small proportion of sulphur-containing compound which provides a sulphur derivative of carbonic acid.

'25. The process ofmaking an adhesive,

comprising reacting upon vegetable protein matter in an aqueous caustic soda-limemedium with a small proportion oi'la sulphur containing compound which provides a sulwith a small proportion of a sulphur-containing compound which provides a sulphurde- 'rivative of carbonic acid.

28. The process of making an adhesive,

comprising reacting upon soya bean protein matter in an aqueous caustic soda-lime me-' 1 .diumwith. a small proportion of a sulphurcontaining compound which provides a sulphur derivatlve of carbonic acid.

comprising subjecting vegetable protein matten to an aqueous .alkaline medium of a strength which will chemically react with such protein matter in the presence of a sm all proportion of carbon bisulphide.

30. The'process'of making an adhesive,

' comprising reacting upon vegetable protein matter in an aqueous caustic soda medium with a small proportion of carbon bisulphide.

31. The. process of making an adhesive, comprising reacting upon vegetable protein matter in an aqueous caustic soda-lime me- 29. The process of making an adhesive,

diunr with a small proportion of carbon bir sulphide 32. The process of making .an adhesive comprising subjecting soya bean protein matter. to an aqueous alkaline medium of a:

strength which will chemically react with such protein matter in the presence of a small proportion of carbon bisul hide.

33. The process of ma g an adhesive, comprising reacting upon soya bean protein matter in an aqueous caustic soda medium with a small proportion of carbon bisulphide.

34. The'process of making an adhesive, comprising reacting upon soya bean protein matter in an aqueous caustic soda-lime"medium with a small proportion of carbon bisulphide.

The process of making an adhesive,

comprising subjecting vegetable protein matter to an aqueous alkaline medium of a strength which will chemically react with such protein matter -'in the presence of a small proportion of a liquid sulphur-com taining compound which provides a sulphur derivativeofcarbomc acid.

36; The process of making an adhesive,

, comprising reacting upon vegetable protein matter in an aqueous caustic soda medium with a small proportion of a liquid sulphur containing compoundwhich provides a sulphur derivative of'carbo'nic acid.

37. The process of making an adhesive,

comprising reacting upon vegetable protein matter in an aqueous caustic soda-lime medium' with a' small proportion of a liquid sulphur-containing compound which provides a sulphur derivative of carbonic acid.

38..The process of making an adhesive, comprising subjecting soya bean protein matterto an aqueous alkaline medium of a strength which will chemically react with such protein matter in the presence of a small proportion of a liquid sulphur containing compound which provides a sulphur derivative of carbonic acid.

' '39. The process of making an adhesive,

-comprising reacting upon soya bean protein matter in an aqueous caustic soda medium with a small proportion of a liquid sulphur-.

containing compound which provides a sulphur derivative of carbonic acid.

40. The process of making an adhesive, comprising reacting upon soya bean protein matter in an aqueous. caustic soda-lime medium with a small proportion of a liquid sul-- I phur-containing compound. which provides a sulphur derivative of carbonic acid.

Signed by us this first day of March, 1927.

IR V [N G F. LAUCKS. GLENN DAVIDSON. 

